CN102803153B - Stable biocidal delivery systems and treatment against biofouling - Google Patents
Stable biocidal delivery systems and treatment against biofouling Download PDFInfo
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- CN102803153B CN102803153B CN201180015289.9A CN201180015289A CN102803153B CN 102803153 B CN102803153 B CN 102803153B CN 201180015289 A CN201180015289 A CN 201180015289A CN 102803153 B CN102803153 B CN 102803153B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/14—Additives which dissolves or releases substances when predefined environmental conditions are reached, e.g. pH or temperature
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Abstract
An improved stabilized biocidal delivery system has been found which increases the efficiency and effectiveness of introducing antimicrobial compounds into complex bio-film matrices through the use of liposome vesicular carriers, thereby removing the bio-fouling in industrial water bearing systems, including piping, heat exchanges, condensers, filtration systems and fluid storage tanks. The improved stabilized biocide is comprised of a vesicle encapsulated biocide that is stabilized against chemical and heat degradation over longer periods of time than previously possible through the incorporation of a stabilizer compound. A method for treating an industrial water system with the delivery composition is also claimed.
Description
the cross reference of related application
According to the 119th article, United States Code the 35th chapter, this application claims the U.S. Provisional Patent Application sequence number submitted on January 21st, 2010 is No.61/297, the right of priority of 026.
Invention field
Put it briefly, the field of the invention relates to the biocide delivery system providing product or compound (such as pharmaceutical chemicals) to industrial system.The invention still further relates to composition, described composition be used in different environments by its targeted delivery to Bacterial biofilms.
background of invention
Bacterial biofilms is present in natural, medical science and industrial environment.Microbial film provides selective advantage to guarantee this microbial survival or to allow them to there is the regular hour in the dormant state until there is suitable growth conditions to microorganism.Unfortunately, this selective advantage is to healthy or cause serious threat to the efficiency of industrial system and life-span.Microbial film must be minimized or be destroyed with the efficiency improving industrial system, or removes potential health threat.
Based on different reasons (such as in order to cooling system), the operation of much industry or business depends on a large amount of water, or described system can produce a large amount of waste water, which results in and needs biomembranous generation to be processed.These industry include but not limited to agricultural, oil, oil drilling, petroleum pipe line, oil storage, Sweet natural gas probing, natural gas line, natural gas storage, chemistry, pharmacy, mining, Metal plating, weaving, papermaking, wine brewing, food and drink processing and semi-conductor industry.In these operations, the microbial film of natural appearance continues to produce and often accumulates in the surface of multiple structure or equipment, or on natural or biological surface.In industrial setting, these biomembranous existence cause the reduction of industrial machinery efficiency, need to improve safeguard and there is potential health risk.The surface of water cooling tower is an example, its cover by ever-increasing microbial film mucus, these microbial film mucus originate from various microorganism, which limit current and reduce the ability of thermal exchange.Particularly, in flowing or the water stagnated, microbial film can cause serious problem, and this comprises microorganism owing to breeding under microbial film and the growth of bacterium and the line clogging caused by growth of potential harmful pathogenetic bacteria and equipment corrosion.The microbial film of water cooling tower can be formed make pathogenic micro-organism (such as legionella pneumophilia (
legionella pneumophila)) hiding-place of permanent growth or storage ground.
Other example of industrial system is those systems in food and drink industry.Food production line is subject to accumulating in the biomembranous puzzlement on machinery and food usually, and wherein microbial film is usually containing potential pathogenic agent.Industrial bio film (microbial film such as found in the food industry) is the polymer of the complexity that the biopolymer of being rich in insoluble polysaccharide is formed, and it is that the microorganism lived by surface produces and builds.More particularly, microbial film or Microbial slime comprise polysaccharide, protein and the lipopolysaccharides of being discharged by certain micro-organisms, make microorganism adhering at the solid surface contacted with water surrounding and are formed in the lasting group of the set bacterium bred in protective membrane.This film can allow anaerobic species to grow, thus produces acid or corrosive atmosphere.For controlling these problems, need the method and the antimicrobial products that control biofilm formation and growth.Biomembranous control relate to prevent microorganic adhesion and/or by existing microbial film by surface removal.Although carry out of short duration clean by using etching reagent or oxygenant to achieve removal under many environment, controlling the biomembranous material the most often used is biocide and dispersion agent.
The United States Patent (USP) 5 of Hollis etc., 411,666 teach and remove microbial film or the methods that prevent microbial film from gathering on solid matrix, and it comprises at least two kinds of biogenic enzymes (such as acid or Sumizyme MP and glucoamylase or α-amylase) and at least one tensio-active agent.The United States Patent (USP) 6 of Manyak etc., 759,040 teaches the method for lytic enzyme mixture preparing microbial film degradation property, polyspecific, this mixture is for removing specific microbial film, and the United States Patent (USP) 5 of Paterson etc., 512,213 metal-salts taught by adding stabilizing amount carry out the method for stable, aqueous solution, and this aqueous solution contains the iso thiazolinium compound that chemical resistance is decomposed.The positively charged ion of described metal-salt is basic metal, and negatively charged ion is selected from acetate moiety, citrate, phosphate radical and borate.
Finally, the United States Patent (USP) 6,267,897 of Robertson etc. relate to a kind of method suppressing biofilm formation in business or industrial water system by adding or vegetable oil in system.But although described biocide effectively controls the microbial suspension (i.e. plankton) disperseed, biocide is not bery effective in the microorganism (biomembranous basis) of set.This is difficult to through this fact of polysaccharide/protein slime layer around microorganism cells owing to biocide.The rarely found biocide of thicker microbial film passes, and result is that effect of biocide is poor.One known, and to attempt to control better biomembranous method be in Biocidal composition, add dispersion agent and wetting agent to strengthen effect of biocide.Bio-dispersant can be used for the dispersion keeping plankton enough, makes them cannot assemble or reach startup and causes the extracellular process of surface anchoring or start film or the necessary local density of group's Forming Mechanism.As the component of biocide treatment agent, these bio-dispersants help in microbial film open wireless tunnel to allow toxic agents to permeate better and to disperse better to be weakened and the germs collect thing discharged by surface and grumeleuse.But bio-dispersant is proved preventing initial biofilm formation comparison from removing more effective by the microbial film existed.In many cases, even if when applying with thing agents of killing livestock, the activity of bio-dispersant also only can by the surface removal of the biomass of 25-30% by biofouling.
Therefore, still also exist clearly efficiently and effectively send the needs of Antimicrobe compound method, this compound can pass existing microbial film and biofilm matrix better, and more effectively kill the microorganism be included in biofilm matrix, thus kill and eliminate microbial film and to prevent in system (such as industrial system) biomembranous follow-up formation or gather.Also need the dirt reducing microfiltration system thing, and provide cleaning and/or the replacing of lower frequency, it will strengthen whole filtration procedure, and this should be solved.
summary of the invention
In an exemplary embodiment, find biocide delivery system, it improves by using liposome vectors efficiency and the validity of Antimicrobe compound being introduced complicated biofilm matrix, and this delivery system can be used in natural, medical science and industrial application.In industrial application, dirt in industrial system can thing (fouling) and be minimized or eliminate by this delivery system, these industrial systems include but not limited to water system, such as pipeline, heat exchanger, condenser, filtering system and medium, and fluid storage tanks.
According to one embodiment of the invention, the liposome containing biocide (such as hydrophilic biocide) is added and is easy to be formed in biofouling thing (bio-fouling) and biomembranous water system.Described liposome, its composition is similar to the outside surface of microorganism cells wall construction or the material of Institute of Micro-biology's feed, and it is easy to be impregnated in the microorganism come across in existing microbial film.Once described liposome is carried secretly by biofilm matrix, then there is the digestion of described liposome, decomposition or degraded, thus release antimicrobial reagent, or the microorganism that biocidal water-based core is wrapped up with microbial film in local reacts.Due to organisms die, polysaccharide/proteic matrix can not get supplementing, and then thus decomposition causes the biofouling thing of aqueous system to reduce.Depend on involved particular system, thus described biomembranous removal or destroy causes the raising of heat exchange (industrial heat exchanger), the increase (strainer or filtering membrane) of flow, the organism of gluey and granular solids and dissolving in the minimizing of micro-filtration film surface deposition, thus reduce frequency and time that film cleans and reduce final replacing, or total surface corrosion situation reducing pipeline, tank, container or other industrial equipments.
Alternative embodiment of the present invention provides delivery system, this system by active delivery to natural, medical science or industrial system, these systems can be selected from sterilant, foodstuff additive and sanitas that corrosion-resistant treatments, agricultural and business room use, chemistry and biology detects, the enhancing of color and taste, smell control and aquatic insect management.
More particularly, the present invention is the improvement to the delivery system described by disclosed PCT application WO 2009/020694 A1, wherein, prepare the liposome biocide delivery system of the antimicrobial system about stabilization, the antimicrobial system of this stabilization comprises Non-oxidizing biocides, such as isothiazoline compounds.Have been found that isothiazoline compounds experiences decomposition under high temperature, high pH, reductive agent and aggressive nucleophilic reagent exist.When adding liposome in isothiazoline solution, the reduction characteristic of lipid is unfavorable for the stable of isothiazoline.Oxidation characteristic and the acidic salt solution (pH1 ~ 3) of isothiazoline class Antimicrobe compound also cause the degraded of liposome and final physical sepn.At elevated temperatures, these degradeds and the process acceleration be separated, create the unsatisfied product being unsuitable for commercial applications.Individually, these biocides usually show after 50 DEG C of next weeks two kinds of materials be greater than 50% degraded.One aspect of the present invention comprises application stability oxidizer composition such as sodium chlorate, and more particularly, comprise the stabilized mixture using damping fluid, these damping fluids are selected from Citrate trianion, oxymuriate, acetate and its mixture.More preferably comprise the stabiliser composition of sodium citrate buffer solution, sodium acetate buffer, sodium chlorate damping fluid, Trisodium Citrate/sodium chlorate buffer solution mixture and sodium acetate/sodium chlorate buffer solution mixture.
Characterize multiple new feature of the present invention highlighted in the claims of enclosing, and constitute a application's part.In order to understand the present invention better, its service advantages and the benefit obtained by its use, the content of reference accompanying drawing and description.Certainly, can change different components of the present invention and replace.The present invention is also the sub-combination of described key element and subsystem and uses their method.
detailed Description Of The Invention
The approximating language that this specification sheets and claims use can be used for modifying any expression quantitatively, and it can allow change under not causing the basic function involved by it to change.Therefore, the numerical value modified by one or more term (such as " about ") be not limited to the exact numerical that limits.In at least some example, this approximating language may correspond to the precision in the instrument measuring this numerical value.Unless linguistic context or language are otherwise noted, scope restriction can in conjunction with and/or exchange, these scopes are clear and definite and comprise wherein included all sub-scope.Except operation example or be otherwise noted, the numeral of all content relating to composition, reaction conditions etc. that use in the specification and in the claims or expression, all should to be understood in all cases modify by term " about ".
Term as used herein " comprises (or comprising) (comprise) ", " comprising (or comprising) (comprising) ", " comprising (includes) ", " comprising (including) ", " having (has) ", " having (having) " or its other variant any, object is to contain comprising of non-exclusive.Such as, comprise the process of a series of key element, method, article or device and need not be only limitted to those key elements, and that other is not clearly listed or that these processes, method, article or device are intrinsic key element can be comprised.
Found delivery system, it improves efficiency and the validity of Antimicrobe compound being introduced complicated biofilm matrix by application liposome vectors, and this delivery system can be used in natural, medical science and industrial application.In industrial application, the dirt in industrial system can thing and be minimized or eliminate by this delivery system, and described industrial system includes but not limited to water system such as cooling tower, pipeline, heat exchanger, condenser, filtering system and medium and fluid storage tanks.
According to one embodiment of the invention, the liposome containing biocidal or antimicrobial reagent or compound is added into and is easy to be formed in biofouling thing and biomembranous industrial system.Its composition of this liposome is similar to microbial film or cell, is easy to mix in existing microbial film.Once should diffuse into containing liposome of Antimicrobe compound, to adsorb or by biofilm matrix entrained with, be present in microorganism in this biofilm matrix then by this liposome structure of digestion, thus cause the decomposition or division that are positioned at the intramatrical liposome of microorganism cells, therefore described Antimicrobe compound is released in microbial cell in matrix, finally causes this microbial death.That is, lipolytic and biocide release are by making lipidic matrix to pH, redox-potential and Ca
+ 2concentration or other change sensitivity control it and occur.Thereafter, the biocidal ingredient that can be concentrated in the water-based core of liposome or the lipid film part of liposome is released, the microorganism direct reaction wrapped up with microbial film.Therefore, not add high-caliber biocide in whole water system, but a small amount of liposomal encapsulated biocide is absorbed by the biological institute of microbial film or free (swimming), the degraded of liposome locally releases biocide at target organism or its membrane matrix microhabitat.Therefore biocide reaches high density in local thus kills this target organism, due to biological death, form biomembranous polysaccharide/proteic matrix cannot maintain or regenerate, and decompose, thus thing in the dirt reducing aqueous system, cause heat exchange raising, flow improve, glue on micro-filtration film with the minimizing of the organic deposition of granular solid and dissolving, thus reduce frequency and the time of Membrane cleaning and reduce final replacing, or bringing other benefit.
Liposome (Liposomes or lipid bodies) lipid is added the system being formed in aqueous buffer solution and hold the balloon-shaped structure of certain volume.Liposome can be formed by being selected from following lipid, and these lipids are phosphatide, Yelkin TTS, phosphatidylcholine, glycolipid, triglyceride level, sterol, lipid acid, sphingophospholipid or its combination.
More particularly, liposome is visible vesicle under microscope, and major part is made up of phosphatide and water usually.Liposome can be obtained by the phosphatide of different sources (including but not limited to soybean and egg).After suitably mixing, phospholipid arrays becomes double-deck or multilayer, is very similar to cytolemma, around aqueous volume core.Liposome can be produced and be positioned at the intracardiac various compound of aqueous core or chemical preparations for carrying, or required compound can be made in suitable carrier to enter lipid layer.Liposome can be made into various size and can be made as diameter is that submicron arrives many microns.Liposome is prepared by several known methods.The evaporation that these methods include but not limited to control, extrude, inject, microfluidic processor and Rotor-stator mixers.Liposome can be prepared to diameter range for about 10 nanometers are to being greater than about 15 microns.When be produced into about 100 nanometers to about 20 microns of sizes time, liposome is similar to size and the composition of most of microbe cell very much.Liposome containing biocide or Antimicrobe compound should be prepared into the size of imitating bacterial cell, for example, and from about 0.05 to about 15 μ, or from about 0.1 to 10.0 μ.The detailed description about method for preparing lipidosome can be obtained, such as United States Patent (USP) 5,807,572 and 7,491,409.These two sections of patents are incorporated herein by reference.
In one embodiment, the liposome containing biocide of significant quantity is introduced into and is easy to be formed in biofouling thing and biomembranous industrial system, maybe can be introduced in the system having existed and formed biofouling thing and microbial film sign.Significant quantity changes with Antimicrobe compound or biocide and the water system that enters added by it, but an embodiment provides from about 0.01ppm to about 100ppm, or from about 0.05 to about 50ppm, or from about 0.05 to about 5.0.Form approximate liposome with microbial film or cell walls to be easy to be incorporated in existing microbial film, and carried secretly in biofilm matrix.Owing to being similar to biomembranous the Nomenclature Composition and Structure of Complexes, the liposome comprising biocide improve to biofilm matrix through property.Once liposome is impregnated in or is entrained into existing biofilm matrix, liposome then starts cracking.Due to decomposition or the procedural cracking of liposome, the Biocidal compounds contained in liposome core water is released, thus directly and the microbial process that wraps up of microbial film, causes their death.Due to organisms die, this polysaccharide/proteic matrix meeting fast decoupled, is discharged contaminating microorganisms by surface.
More particularly, one aspect of the present invention relates to liposomal encapsulated biocide delivery system, wherein non-oxidizable Biocidal compounds stablize by Citrate trianion/oxymuriate buffer compositions, wherein the stability that provides biocide actives of this cocktail buffer is eager to excel a lot than any one damping fluid separately.The principal feature of one embodiment of the invention is that liposome constitutes minimum hydrophobic body, can easily survive in system (such as water system or natural system) and dispersion, also will be adsorbed to or through microbial film and preferred direction in microorganism or directed by Institute of Micro-biology, wherein these colonisation in, form or maintain this microbial film.Because so, liposome will kill biological reagent and directly be delivered to microorganism or microbial film, cause effective local biocide activity level, and do not need industrial system entirety to maintain high dosage.Therefore, the process of traditional biological film may need (bulk) in bulk that use certain level to kill bio-chemical, then can with low one or the order of magnitude or low more level administration in water system by liposome delivery, but still can realize or set up and effectively control or remove biomembranous level.Due to the effect having this delivery system to cause, this lower level biocide density has positively effect to environment.In addition, based on pending particular system, embodiment provides liposome by the handiness be in fact delivered in system.If a specific region in system be easy to formed microbial film, then liposome send this specific part or point that can be delivered to this system, sending of such biocide delivering compositions is delivered to the fixed position of target, need not participate in or be exposed to whole system.Due to effect of the biocide of this form, need the liposome containing biocide of smaller dose, thus whole system or method do not need to be full of by biocide or to process.
In fact, although term " biocide " or " biocide " or " biocidal " are used to describe the reagent carried by liposome, but these reagent need not to be the material by usual the understood high biological activity of these terms, but the material of a large amount of relative harmless can be comprised, these materials only become efficient due to the release of their height local.Therefore, for example, when locally being discharged, the halide salt of tensio-active agent or harmless An Huo Phosphonium can affect the normal effect that extracellular bacterium colony forms secretion, and be included as the biocide of the object of the invention or biocide, the microbial film position that other process pharmaceutical chemicals is delivered to target by identical mechanism can be applied.
The water system of available the method process includes but not limited to tap water and undrinkable water distribution system, cooling tower, boiler systems, shower bath, aquarium, sprinkler system, hot spring, clean bath, gas purifier, pasteurisation appts, air-conditioning, liquid conducting pipes, storage tank, ion exchange resin, food and drink production line, intermetallic composite coating liquid bath, coal and slurry of mineral, metal leach liquor, sewage treatment equipment, mollusk controls, paper pulp and paper-making operation, acid ore deposit draining or any application being easy to the biofouling caused by microbe species.(wherein biofilm formation also can be processed in the puddle of assembling along the immobilising of tubing system or current or protuberance (lenses) in the application of such as oil drilling, petroleum storage tank or petroleum pipe line.
Other application through liposome delivery process pharmaceutical chemicals comprise natural, medical science or industrial system, these systems are such as, but not limited to common equipment corrosion-resistant treatments, send for medical science or animal doctor's object hormone, VITAMIN or antioxidant process or antibiosis and gene therapy, send the sterilant for agricultural and business room, effective preparation of foodstuff additive and sanitas, the targeted delivery that chemistry and biology detects, the enhancing of color and taste, smell controls, and the management of aquatic insect.
Antimicrobial liposome is such system, and lipid is added to form balloon-shaped structure in the Antimicrobe compound solution of water-based within the system, and this structure holds a part of antimicrobial solutions.Liposome can be formed by being selected from following lipid: phosphatide, Yelkin TTS, phosphatidylcholine, glycolipid, triglyceride level, sterol, lipid acid, sphingophospholipid or its combination.
As what simply mention above, existing document proves that isothiazoline carries out decomposition under high temperature, high pH, reductive agent and aggressive nucleophilic reagent exist.When liposome is added into isothiazoline solution, the reduction characteristic of lipid is unfavorable for the stable of isothiazoline.And the oxidation characteristic of isothiazoline Antimicrobe compound and acidic salt solution (pH1 ~ 3) also cause liposome to degrade and final physical is separated.At elevated temperatures, these degradeds and sepn process are accelerated, and produce the unsatisfied product being not suitable for commercial applications.
One aspect of the present invention is included in isothiazoline liposome composition the combination adding Citrate trianion, acetate or oxymuriate buffer components, with the pH of regulator solution and redox-potential.Result be the opposing decomposition of stabilization Synergistic microbicidal compositions and without the homogeneous phase liposome solutions that physics is separated, reach degree that is astonishing and that strengthen unexpectedly, exceeded the effect that arbitrary compound is used alone.Although any type of salt can be used in theory, due to any one in many reasons, particular certain cancers form.
In order to prepare the antimicrobial liposome of isothiazoline, add lipid to form liposomal vesicle in isothiazoline solution, it encloses a part and is dissolved in iso thiazolinium compound in solution.Isothiazoline and liposome are stable respectively.Commercial isothiazoline product such as R & H Kathon stablizes through magnesium nitrate.Commercial phosphatide and Yelkin TTS such as Cargill Lecigran stablize through tocopherol.But when mixing, iso thiazolinium compound is incompatible with liposome.Magnesium nitrate and tocopherol cannot provide enough stabilizations, and result in when pH drops to lower than 1.7 and temperature rises to higher than 35 DEG C, 3-isothiazoline chemical degradation and Liposomes are irreversibly separated from isothiazoline solution.Need to add additional stability agent and deal with these problems.In one embodiment, the present invention's application citrate buffer solution and oxymuriate are guaranteed the consistency of product as additional stability agent and are extended the shelf life.Suitable stablizer Laemmli buffer system Laemmli comprises Trisodium Citrate, sodium chlorate, sodium acetate and composition thereof.
Various types of biocide (such as Non-oxidizing biocides) can be impregnated in liposome and to be effective.Preferably, can be used for implementing Non-oxidizing biocides of the present invention is isothiazoline, more preferably 3-isothiazoline.With to be introduced in system but compared with the identical isothiazoline-3-ketone compound not mixing the identical active concentration of liposome, these isothiazolines-3-ketone Liposomal formulation kill and remove in microbial film more effective because the liposome containing biocide is easily through the microbial film of microorganism and disrupting biofilm matrix efficiently.This liposome delivery method can comprise CMIT and MIT, but when kill at liposome send in Biodelivery systems or composition time, any biocide of isothiazoline-3-ketone based on replacing can be made more efficient significantly.
The example of isothiazoline-3-ketone compound is
Comprising the of the present invention of isothiazoline in preparation kills livestock in composite lipidosome process, and active iso thiazolinium compound, with from about 1.0wt% to the amount of about 12.0wt%, preferably from about 10.0wt% to the amount of about 12.0wt%, is impregnated in liposome.Mix the amount of the stability buffer composition in Liposomal formulation from about 0.02wt% to about 10.0%wt%, preferably from about 0.03wt% to the amount of about 5.5wt%.The mixture of the particle of the normally different size of this Liposomal formulation.Although the high liposome particles to 200 microns of sizes can be prepared, be preferred for implementing the size of liposome of the present invention in the scope of diameter about 100 nanometer to about 10 microns.
Liposome of the present invention can be made into polylayer forest, wherein provides one or more extra play, the lipid conformation body based on the stability strengthening liposome or realization and the procedural release of content.Therefore, this technology can be used for entrapped drug and sends in body, and described like this extra play can comprise protective layer, and protective layer is hydrolyzed after a certain time or otherwise decomposes to provide sustained release or the prolongs life of basic liposome.This extra play can also comprise packing polymer, and it optionally decomposes when meeting with low pH environment when multilamellar liposome, and this low pH environment is as corrosive peracidity environment that can be formed under microbial film.
Layer can also be made and easily be destroyed by solid thiobacterium, thus cause liposome often to appear at those biocide discharging it near corrosive biological in waste and old or tubing system specifically.And, several layer like this can be applied to guarantee the ability of specific microhabitat or environment in the life-span (preferred a couple of days) that liposome is enough and target biology film.Which ensure that lipid physical efficiency effectively arrives target organism or microbial film bacterium colony and their biocide is delivered to target organism or microbial film bacterium colony.This matrix material itself can be treated with the resistivity provided hydrolysis or rotten enhancing, or these additional layers can be formed by different sclerosis or crosslinkable oil or polymer.
Alternative embodiment of the present invention is provided at least one antimicrobial composition being delivered to the biomembranous biocide delivering compositions be present in industrial system, and wherein this microbial film comprises at least one microbial species; B) this biocide delivering compositions comprises the liposome structure containing at least one lipid or phospholipid composition; And c) this liposome structure encapsulates the non-oxidizable antimicrobial composition of at least one of combining with stabiliser composition.
Other embodiments, by the biocide of significant quantity being introduced the important area in industrial system (such as industrial water system), provide the targeted delivery in described biocide active delivery to described system.In method, determine a certain region by target and enter specific site, effect of liposome system significantly affects the cost of environment and maintenance system, because whole system does not need to fill biocide, and only need in specific target area.
To describe more specifically the present invention in the following embodiments and describe in detail now, carry out how best to illustrate better to those skilled in the art and implement scope of the present invention.It is emphasized that they only for illustration of object, should not be interpreted as the restriction to the spirit and scope of the present invention stated in the following claims.
Embodiment
Prepared the liposome (mean diameter 150 nanometer) of three batches, liposome is mixed with the isothiazoline biocide Kathon (can by Rohm & Haas, Philadelphia, PA obtain) as activeconstituents.Then this liposome is put into the microtiter plate covering microbial biofilm.Then the isothiazoline biocide of Antimicrobial effect of isothiazoline liposome with the non-liposomal used with identical isothiazoline concentration is compared.Liposome containing isothiazoline is through microbial film and the effect of suppression biological membrane biological is more much effective than the isothiazoline solution of non-liposomal.Liposome containing biocide is made up of the following compositions separately for percentage ranges:
composition
percentage ratio (% weight)
A) KATHON 886F (14.0% isothiazoline) 78.67
B) deionized water 0.67
c)LECIGRAN? 6000G 10.0
D) sodium chlorate (50% solution) 8.0
E) two citric acid monohydrate sodium 2.33
F) monohydrate potassium 0.33
The degraded of 3-isothiazoline liposome carrys out quantitative observation by the formation of insoluble precipitate.Application quantitative gas chromatography (GC) and high pressure liquid chromatography (HPLC) analysis measure the activity component concentration being stored in the sample accelerated under storage environment (50 DEG C).The stability of isothiazoline liposome known in the art is as described below.
At 38 DEG C and 50 DEG C, test has the different isothiazoline preparation of stablizer.From following table 1, citrate buffer solution and oxymuriate stablizer be combined in 38 DEG C/100 ℉ under preservation period was extended to 85 days by 29 days, and preservation period is only extended to 49 days and 42 days by independent citrate buffer solution or oxymuriate respectively.With the composition below shown in table 1 than the antimicrobial liposome composition having prepared 13 kinds of stabilizations.These liposomes being mixed with the encapsulating isothiazoline of different damping fluid stabilizer compounds compare to the irreversible stability be separated after for some time at 4 kinds of different temperature with number of days, as follows:
From this table, Trisodium Citrate/sodium chlorate buffer composition adds separately the stability providing unexpectedly high-caliber liposome Biocidal composition than arbitrary damping fluid.The stability of the antimicrobial liposomal compound become with pH after determining for some time.Although show separately the stability of good biocide containing isothiazoline/sodium acetate buffer and the liposome separately containing isothiazoline/citrate buffer solution, 42 days and 49 days are respectively under 38 DEG C/100 ℉, but the combination containing sodium acetate/sodium chlorate damping fluid and the liposome of isothiazoline biocide and show the stability of the biocide of surprising excellence containing the combination of Trisodium Citrate/sodium chlorate damping fluid and the liposome of isothiazoline biocide, be respectively 51 days and 85 days at the temperature of identical rising.
Except above-described, this biocide can be the biocide being suitable for killing or destroying target microorganism of any type.In one embodiment, this biocide can be non-oxidizable or oxidative compound, or its combination.In further embodiment, this biocide comprises but is not limited to guanidine class or biguanides salt, quaternary ammonium salt, phosphonium salt, 2-bromo-2-nitro third-1,3-glycol, CMIT/MIT, chlorination alkyl-dimethyl benzyl ammonium, 2,2, two bromo-3-nitrilo propionic acid amide methylene radical-bis-(thiocyanic ester), hydrochloric acid Cyprex, glutaraldehyde, 2-(tert-butylamino)-4-chloro-6-(ethylamino)-s-triazine, Beta-bromo nitrostyrolene, tributyltin oxide, n-tributyl tetradecane Ji phosphonium chloride, tetrakis hydroxymethyl phosphonium chloride, 4,5 ,-two chloro-1,2 ,-dimercapto-3-ketone, Sodium dimethyldithiocarbamate 40min, ethylenebis (nabam), two (trichloromethyl) sulfone, 3,5-dimethyl-tetrahydro-2H-1,3,5 ,-thiadiazine-2-thioketones, 1,2 ,-benzisothiazole-3-ketone, hydrochloric acid decyl thioethylamine, copper sulfate, Silver Nitrate, bromo-chloro-dimethyl hydantoin, Sodium Bromide, dichlorodimethylhydantoin, clorox, hydrogen peroxide, dioxide peroxide, Textone, bromine chloride, peracetic acid and precursor thereof, TCCA (Trichloroisocyanuric acid) sodium, TCCA (Trichloroisocyanuric acid) sodium, dibromo, dicyanobutane and combination.
In one embodiment, this biocide can be guanidine class or biguanides salt, quaternary ammonium salt He phosphonium salt.The example of guanidine class or biguanides salt has following general formula:
or
or
Wherein, R, R
1, R
2h, C independently
1-C
20substituted or non-substituted alkyl (straight or branched) or aryl, X is organic acid or mineral acid, and n is 0-20 and z is 1-12.
The Ke Jie of described general formula comprises (R Shou the example of phosphonium salt
1)
3p
+r
2● X
-, wherein R
1the alkyl of 1-8 carbon atom, R
2be the alkyl of 8-20 carbon atom, X is the negatively charged ion be made up of halogen ion, sulfate radical, nitrate radical, nitrite anions and combination thereof.
Alternative structural formula defines R
1the alkyl with 1-8 carbon atom, R
2the alkyl with 8-20 carbon atom, X
-negatively charged ion, such as halogen ion, sulfate radical, nitrate radical, nitrite anions and composition thereof.Preferably, X
-chlorine, bromine, iodine, SO
4 =and NO
3 -, NO
2 -or its mixture.
Other embodiment defines R
1and R
2the hydroxyalkyl with 1-4 carbon, X
-negatively charged ion, such as halogen ion, sulfate radical, nitrate radical, nitrite anions and composition thereof.Preferably, X
-chlorine, bromine, iodine, SO
4 =and NO
3 -, NO
2 -or its mixture.
Quaternary ammonium salt is can encapsulated or other example of being prepared in liposome core, and it has general formula
R
1r
2r
3n
+--CH
2-phenmethyl ring X
-
Wherein, R
1be chain length be C
8– C
18alkyl, R
2and R
3cH
3or chain length is C
2– C
8alkyl, X
-negatively charged ion, such as halogen ion, sulfate radical, nitrate radical, nitrite anions and its mixture.
Non-biocidal reagent can be eco-friendly compound or the composition of any type, and it is removed or deactivation protozoon spread to prevent it, such as, by disturbing protozoic life cycle or the breeding cycle removes or deactivation protozoon.In one embodiment, non-biocidal reagent can be used as auxiliary and applies together with biocide.For example, non-biocidal reagent includes but not limited to bio-dispersant, ethylene oxide/propylene oxide multipolymer, trichlorine caproic acid, polysiloxane, carbon silane, polymine, bacterium, microorganism, plasmid, phagocytic cell, scavenger cell, toxin producing microorganism, amino acid, protein, peptide, DNA, RNA, base pair, sense-rna medicine, microbiotic, sequestrant, natural extract, organic/inorganic redox agent, organic and inorganic dyestuff sensitizing agent, antiapoptotic signals transduction agent, the extract of microorganism and plant derivation and by product, Metabolite, sanitas, poisonous plants chemical, microbial toxin, produce the catalyzer of free radical or active oxygen, CYSTINE and enzyme or its combination.
Biocide and stablizer can the amount of any enough this microorganisms of control mix in vesicle, and depend on the selection of specific biocide and stablizer.In one embodiment, the amount of biocide in liposomal vesicle or non-biocide of mixing, for about 1.0wt%-12wt%, mixes the amount of the stablizer in vesicle for about 0.02-10.0wt%.
In one embodiment, vesicle adds in water system with significant quantity, to make the amount of the biocide in this water system of introducing for about 0.05 to about 500 micrograms/ml.In further embodiment, vesicle adds in water system to make the amount of the biocide in this water system of introducing for about 0.1 to about 100 micrograms/ml.In further embodiment, the amount of the vesicle in water system is added for about 0.01ppm to about 50ppm (volume).In further embodiment, the amount of the vesicle in water system is added for about 0.01ppm to about 20ppm (volume).In further embodiment, the amount of the vesicle in water system is added for about 0.05ppm to about 5.0ppm (volume).
Except above-named exemplary stablizer, other can comprise by referred stablizer:
A) KIO
3, HIO
3, Periodic acid (periodic), periodate (periodate salts)
B) Jin Shu Xiao Suan Yan – Na, K, Ca, Mg
C) ortho ester-trimethyl orthoformate, positive formic acid triethyl, triethly orthoacetate, original acid methyl ester, former phenylformic acid trimethyl
D) Form aldehyde release
E) phenoxy group alkanol-phenoxyethyl alcohol, phenoxy group Virahol
F) based on heterocyclic thiol-2 mercaptopyridine of nitrogen, MTZ,
2-sulfo-hydantoin, CYSTINE
g) EDTA
H) rheology modig agents, as thickening material
I) stearic steric hindrance agent (stearic hindrance agents) (long-chain repulsion)
J) yield value (yield value) modifies (carbon is as suspension agent)
According to one embodiment of the invention, provide the biocide delivering compositions of stabilization, for being delivered to by least one antimicrobial composition in the microbial film that is present in industrial system.Containing at least one microorganism in this microbial film, this biocide delivering compositions contains liposome balloon-shaped structure, and this structure contains at least one lipid or phospholipid composition.And this liposome structure encapsulates at least one antimicrobial composition of combining with at least one stablizer.Other side of the present invention, this lipid is be selected from following member: phosphatide, Yelkin TTS, phosphatidylcholine, glycolipid, triglyceride level, sterol, lipid acid, sphingophospholipid or its combination.Of the present invention in some, phosphatide can from soybean or egg.In addition, Yelkin TTS can be the mixing of lipid.
According to exemplary embodiment of the subject disclosure, this antimicrobial composition contains at least one biocide, such as Non-oxidizing biocides.For example, this biocide can be iso thiazolinium compound.More particularly, this isothiazoline biocide can comprise and is selected from least one following member: CMIT, MIT or its arbitrary combination.
In the embodiment that other is exemplary, this stablizer or compound are the damping fluids of the mixture comprising two or more compounds being selected from Citrate trianion, oxymuriate damping fluid and acetate.This stabilizer compounds damping fluid can comprise the damping fluid of the metal-salt being selected from citric acid/chloric acid, the damping fluid of the metal-salt of acetic acid/chloric acid and two or more compounds of citric acid/acetate buffer.This damping fluid stablizer can be selected from sodium citrate buffer solution, sodium acetate buffer, Trisodium Citrate/sodium chlorate buffer solution mixture and sodium acetate/sodium chlorate buffer solution mixture.The amount that this damping fluid stablizer can account for about 0.2% to about 10% of total biocide liposome composition is mixed together with isothiazoline biocide, more preferably, the amount of this isothiazoline biocide about 1.0wt% to about 12.0wt% that can account for total biocide liposome composition is impregnated in.Even more preferably, the amount of this isothiazoline biocide about 10.0wt% to about 12.0wt% that can account for total biocide liposome composition is impregnated in.The diameter of this liposome structure can reach about 200 microns, and preferred diameter is between about 100 nanometers are to about 10 microns.This industrial system can be water system.This industrial system can be selected from water distribution system, cooling tower, boiler systems, shower bath, aquarium, sprinkler system, hot spring, clean bath system, gas purifier, pasteurisation appts, air-conditioning, liquid conducting pipes, storage tank, ion exchange resin, food and drink production line, paint spray booth, intermetallic composite coating liquid bath, coal and slurry of mineral, metal leach liquor, sewage treatment equipment, paper pulp and papermaking suspension, mollusk controls, acid ore deposit draining, petroleum drilling inserting tube, petroleum pipe line, petroleum storage tank, Sweet natural gas drill pipe, natural gas line or be easy to any industrial application that the biofilm formation of microorganism induction or the corrosion of microorganism induction occur.
Other side of the present invention, disclose the biomembranous method be delivered to by antimicrobial composition in industrial system, comprise step below: a) the preparation encapsulating at least one liposome balloon-shaped structure of isothiazoline antimicrobial composition of combining with damping fluid stablizer, this damping fluid stabilizer package is containing the mixture of two or more compounds being selected from Citrate trianion, oxymuriate and acetate; And b) introducing from previous step liposome a) of significant quantity is easy to be formed in biofouling thing or biomembranous industrial system.This liposome structure can be introduced into the amount of about 100ppm by about 0.01ppm.In addition, this liposome structure can be introduced into the fixed position of some target in industrial system.This liposome structure can comprise such as isothiazoline biocide, and this isothiazoline biocide can be selected from CMIT, MIT and composition thereof.
This damping fluid stablizer can be selected from sodium citrate buffer solution, sodium acetate buffer, Trisodium Citrate/sodium chlorate buffer solution mixture and sodium acetate/sodium chlorate buffer solution mixture.In addition, the amount of this damping fluid stablizer about 0.2wt% to about 10wt% that can account for total biocide liposome composition is mixed.In other embodiment, the amount that this isothiazoline biocide can account for the about 1.0wt% to about 12.0wt% of total biocide liposome composition is mixed.
Claims (23)
1. at least one antimicrobial composition is delivered to the biocide delivering compositions of the biomembranous stabilization be present in industrial system, wherein
A) described microbial film comprises at least one microbial species;
B) described biocide delivering compositions comprises balloon-shaped structure, and
C) described balloon-shaped structure encapsulates at least one antimicrobial composition of combining with at least one stabiliser composition,
Wherein said antimicrobial composition comprises isothiazoline biocide, and
Described stabiliser composition is sodium citrate buffer solution or sodium acetate buffer, or described stabiliser composition comprises the mixture of two or more compounds being selected from Citrate trianion, oxymuriate damping fluid and acetate,
Wherein said balloon-shaped structure comprises the liposome structure containing at least one lipid composition.
2. biocide delivering compositions as claimed in claim 1, wherein said lipid is be selected from phosphatide, glycolipid, triglyceride level, sterol, lipid acid or its member combined.
3. biocide delivering compositions as claimed in claim 2, wherein said phosphatide is Yelkin TTS or sphingophospholipid or its combination.
4. biocide delivering compositions as claimed in claim 2, wherein said lipid is phosphatide.
5. biocide delivering compositions as claimed in claim 4, wherein said phosphatide is from soybean or egg.
6. biocide delivering compositions as claimed in claim 3, wherein said Yelkin TTS is mixture.
7. biocide delivering compositions as claimed in claim 2 or claim 3, wherein said isothiazoline biocide comprises CMIT, MIT or its combination.
8. biocide delivering compositions as claimed in claim 7, wherein said stabiliser composition is damping fluid, and described damping fluid comprises the mixture of two or more compounds being selected from Citrate trianion, oxymuriate damping fluid and acetate.
9. biocide delivering compositions as claimed in claim 8, wherein said stabiliser composition is damping fluid, and described damping fluid comprises the mixture of two or more compounds being selected from the metal-salt damping fluid of citric acid/chloric acid, the metal-salt damping fluid of acetic acid/chloric acid and Citrate trianion/acetate buffer.
10. biocide delivering compositions as claimed in claim 7, wherein said stabiliser composition is selected from sodium citrate buffer solution, sodium acetate buffer, Trisodium Citrate/sodium chlorate buffer solution mixture and sodium acetate/sodium chlorate buffer solution mixture.
11. biocide delivering compositions as claimed in claim 10, wherein said stabiliser composition mixes together with described isothiazoline biocide with the amount accounting for the 0.2wt% to 10wt% of total biocide delivering compositions.
12. biocide delivering compositions as claimed in claim 11, wherein said isothiazoline biocide mixes with the amount of the 1.0wt% to 12.0wt% accounting for total biocide delivering compositions.
13. biocide delivering compositions as claimed in claim 12, wherein said isothiazoline biocide mixes with the amount of the 10.0wt% to 12.0wt% accounting for total biocide delivering compositions.
14. biocide delivering compositions as claimed in claim 13, the diameter of wherein said liposome structure 200 microns at the most.
15. biocide delivering compositions as claimed in claim 14, the diameter of wherein said liposome structure is between 100 nanometers to 10 micron.
16. biocide delivering compositions as claimed in claim 15, wherein said industrial system is water system.
17. biocide delivering compositions as claimed in claim 16, wherein said industrial system is selected from water distribution system, cooling tower, boiler systems, shower bath, aquarium, sprinkler system, hot spring, clean bath system, gas purifier, pasteurisation appts, air-conditioning, liquid conducting pipes, storage tank, ion exchange resin, food and drink production line, paint spray booth, intermetallic composite coating liquid bath, coal and slurry of mineral, metal leach liquor, sewage treatment equipment, paper pulp and papermaking suspension, mollusk controls, acid ore deposit draining, petroleum drilling inserting tube, petroleum pipe line, petroleum storage tank, Sweet natural gas drill pipe or natural gas line.
18. biocide delivering compositions as claimed in claim 16, wherein said industrial system is selected from any industrial application being easy to the biofilm formation of microorganism induction or the corrosion of microorganism induction occur.
Antimicrobial composition to be delivered to the biomembranous method in industrial system by 19., described method comprises step below: a) liposome structure of the antimicrobial composition of at least one isothiazoline biocide of combining with damping fluid stablizer is encapsulated in preparation, this damping fluid stablizer is sodium citrate buffer solution or sodium acetate buffer, or this damping fluid stabilizer package is containing the mixture of two or more compounds being selected from Citrate trianion, oxymuriate and acetate; And b) introducing from previous step liposome a) of significant quantity is easy to be formed in biofouling thing or biomembranous industrial system.
20. methods as claimed in claim 19, wherein said liposome structure is introduced into 0.01ppm to 100ppm.
21. methods as claimed in claim 20, wherein said liposome structure is introduced into described industrial system and hits fixed position.
22. methods as claimed in claim 21, wherein said isothiazoline biocide is selected from CMIT, MIT and composition thereof.
23. methods as claimed in claim 22, wherein said damping fluid stablizer is selected from sodium citrate buffer solution, sodium acetate buffer, Trisodium Citrate/sodium chlorate buffer solution mixture and sodium acetate/sodium chlorate buffer solution mixture.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29702610P | 2010-01-21 | 2010-01-21 | |
| US61/297026 | 2010-01-21 | ||
| US61/297,026 | 2010-01-21 | ||
| US12/868,377 | 2010-08-25 | ||
| US12/868377 | 2010-08-25 | ||
| US12/868,377 US20110177147A1 (en) | 2010-01-21 | 2010-08-25 | Stable biocidal delivery systems |
| PCT/US2011/020432 WO2011090830A1 (en) | 2010-01-21 | 2011-01-07 | Stable biocidal delivery systems and treatment against biofouling |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102803153A CN102803153A (en) | 2012-11-28 |
| CN102803153B true CN102803153B (en) | 2015-05-13 |
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ID=44277739
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| CN201180015289.9A Expired - Fee Related CN102803153B (en) | 2010-01-21 | 2011-01-07 | Stable biocidal delivery systems and treatment against biofouling |
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| Country | Link |
|---|---|
| US (1) | US20110177147A1 (en) |
| EP (1) | EP2526064A1 (en) |
| CN (1) | CN102803153B (en) |
| AU (1) | AU2011207795A1 (en) |
| TW (1) | TW201130744A (en) |
| WO (1) | WO2011090830A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8784659B2 (en) * | 2007-08-08 | 2014-07-22 | General Electric Company | Method for controlling microbial biofilm in aqueous systems |
| CA2857604A1 (en) | 2011-12-22 | 2013-06-27 | Nuvo Research Gmbh | Liposomal chlorite or chlorate compositions |
| DE102012005380A1 (en) | 2012-03-16 | 2013-09-19 | Daimler Ag | Filter medium useful for filtering air for a interior of a vehicle, comprises a filter layer and a biocide layer comprising micro capsules made of a polymer, where a biocide is stored on and/or in the microcapsules |
| WO2013155691A1 (en) * | 2012-04-19 | 2013-10-24 | General Electric Company | A method to stabilize liposome emulsions for biocidal delivery |
| CN104556429B (en) * | 2013-10-24 | 2017-03-22 | 中国石油化工股份有限公司 | Water treatment medicament composition and application thereof |
| CN104556430A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Water treatment pharmaceutical composition and application thereof |
| CN104761044B (en) * | 2014-01-08 | 2017-02-15 | 中国石油化工股份有限公司 | Water treatment agent composition and applications thereof |
| CN104761066B (en) * | 2014-01-08 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of water treatment agent composition and its application |
| US10058542B1 (en) | 2014-09-12 | 2018-08-28 | Thioredoxin Systems Ab | Composition comprising selenazol or thiazolone derivatives and silver and method of treatment therewith |
| CN104746005A (en) * | 2015-03-17 | 2015-07-01 | 厦门建霖工业有限公司 | Method for preparing antibacterial film on surface of bathroom product |
| EP3450623B1 (en) * | 2017-08-29 | 2023-06-28 | Kemira Oyj | Method for controlling growth of microorganisms and/or biofilms in an industrial process |
| PT3450626T (en) | 2017-08-29 | 2020-07-31 | Univ Copenhagen | Method for controlling growth of microorganisms and/or biofilms in an industrial process |
| CN111072145A (en) * | 2018-10-19 | 2020-04-28 | 上海申英环保科技有限公司 | Ammonia nitrogen remover |
| CN110408440B (en) * | 2019-07-24 | 2021-08-10 | 上海鼎燃节能科技有限公司 | Energy-saving additive for steam boiler and application thereof |
| CN110316792B (en) * | 2019-07-31 | 2024-01-19 | 西安西热水务环保有限公司 | High-speed mixed bed water distribution device capable of preventing resin from flowing backwards |
| CN110482623B (en) * | 2019-09-12 | 2021-08-10 | 上海鼎燃节能科技有限公司 | Temperature regulating system energy-saving agent using water as heat exchange medium and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5478797A (en) * | 1994-11-21 | 1995-12-26 | Rohm And Haas Company | Bromate stabilization of nitrate-free 3-isothiazolones at pH 4-5.1 |
| EP0729703A1 (en) * | 1995-03-01 | 1996-09-04 | Betz Laboratories Inc. | Aqueous isothiazolone solutions stabilized by alkali metal salts |
| US5569464A (en) * | 1993-04-02 | 1996-10-29 | Wakamoto Pharmaceutical Co., Ltd. | Stable aqueous dispersions containing liposomes |
| US5955486A (en) * | 1997-10-28 | 1999-09-21 | Rohm And Haas Company | Stable microbicide formulation |
| CN101820752A (en) * | 2007-08-08 | 2010-09-01 | 通用电气公司 | Method for controlling protozoa that harbor bacteria |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5807572A (en) * | 1988-02-18 | 1998-09-15 | Depotech Corporation | Multivesicular liposomes having a biologically active substance encapsulated therein in the presence of a hydrochloride |
| EP0525166B1 (en) * | 1991-02-12 | 1995-08-09 | Buckman Laboratories International, Inc. | Composition and methods for removing or preventing biofilm |
| EP1017427B1 (en) * | 1997-08-26 | 2006-04-26 | Board of Regents, The University of Texas System | Use of a composition comprising a chelating agent and an antimicrobial compound for the treatment of biofilms |
| US6759040B1 (en) * | 1997-09-12 | 2004-07-06 | University Of Maryland, College Park | Preparation and use of biofilm-degrading, multiple-specificity, hydrolytic enzyme mixtures |
| US6008238A (en) * | 1997-10-28 | 1999-12-28 | Rohm And Haas Company | Stabilization of 3-isothiazolone solutions |
| KR20010112301A (en) * | 1999-03-02 | 2001-12-20 | 질레스피 카롤 | Encapsulation of bioactive complexes in liposomes |
| US6267897B1 (en) * | 2000-05-04 | 2001-07-31 | Nalco Chemical Company | Method of inhibiting biofilm formation in commercial and industrial water systems |
| UA80248C2 (en) * | 2000-06-29 | 2007-09-10 | Compounds and compositions for delivering active agents | |
| US20030194445A1 (en) * | 2001-11-12 | 2003-10-16 | Kuhner Carla H. | Compositions and methods of use of peptides in combination with biocides and/or germicides |
| US7008545B2 (en) * | 2002-08-22 | 2006-03-07 | Hercules Incorporated | Synergistic biocidal mixtures |
| JPWO2006095798A1 (en) * | 2005-03-09 | 2008-08-14 | サンスター株式会社 | Oral composition for anticancer containing liposome containing phytosterol, prevention or treatment of cancer by the liposome |
| EP1797895A1 (en) * | 2005-12-16 | 2007-06-20 | Pevion Biotech Ltd. | An adjuvant system comprising virosomes and liposomes |
| US20070196359A1 (en) * | 2006-02-23 | 2007-08-23 | Minntech Corporation | Halosuccinimide biocide |
| AU2007351886A1 (en) * | 2006-06-23 | 2008-10-30 | Paratek Pharmaceuticals, Inc. | Transcription factor modulating compounds and methods of use thereof |
| US7824557B2 (en) * | 2007-08-08 | 2010-11-02 | General Electric Company | Method for controlling microbial biofilm in aqueous systems |
| EP2408307A1 (en) * | 2009-03-20 | 2012-01-25 | General Electric Company | Biodelivery systems |
-
2010
- 2010-08-25 US US12/868,377 patent/US20110177147A1/en not_active Abandoned
-
2011
- 2011-01-07 CN CN201180015289.9A patent/CN102803153B/en not_active Expired - Fee Related
- 2011-01-07 WO PCT/US2011/020432 patent/WO2011090830A1/en active Application Filing
- 2011-01-07 AU AU2011207795A patent/AU2011207795A1/en not_active Abandoned
- 2011-01-07 EP EP11702720A patent/EP2526064A1/en not_active Withdrawn
- 2011-01-21 TW TW100102353A patent/TW201130744A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5569464A (en) * | 1993-04-02 | 1996-10-29 | Wakamoto Pharmaceutical Co., Ltd. | Stable aqueous dispersions containing liposomes |
| US5478797A (en) * | 1994-11-21 | 1995-12-26 | Rohm And Haas Company | Bromate stabilization of nitrate-free 3-isothiazolones at pH 4-5.1 |
| EP0729703A1 (en) * | 1995-03-01 | 1996-09-04 | Betz Laboratories Inc. | Aqueous isothiazolone solutions stabilized by alkali metal salts |
| US5955486A (en) * | 1997-10-28 | 1999-09-21 | Rohm And Haas Company | Stable microbicide formulation |
| CN101820752A (en) * | 2007-08-08 | 2010-09-01 | 通用电气公司 | Method for controlling protozoa that harbor bacteria |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2526064A1 (en) | 2012-11-28 |
| US20110177147A1 (en) | 2011-07-21 |
| AU2011207795A1 (en) | 2012-08-09 |
| WO2011090830A1 (en) | 2011-07-28 |
| CN102803153A (en) | 2012-11-28 |
| TW201130744A (en) | 2011-09-16 |
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